Fungicidal composition containing n-(alpha-cyano-2-thenyl)-4-ethyl-2-(ethylamino)-5-thiazolecarboxamide

ABSTRACT

The present invention relates to a fungicidal composition which comprises N-(α-cyano- 2 -thenyl,) 4 -ethyl- 2 -(ethylamino)- 5 -thiazolecarboxamide(ethaboxam) and as an adjuvant polyoxyalkylene alkyl ether.

TECHNICAL FIELD

[0001] The present invention relates to a novel fungicidal compositioncomprising a 2-aminothiazolecarboxamide derivative,N-(α-cyano-2-thenyl)-4-ethyl-2-(ethylamino)-5-thiazolecarboxamide (ISOproposed name: ethaboxam) of the formula:

[0002] , and as an adjuvant a suitable nonionic surfactant.

BACKGROUND ART

[0003] A compound of formula (I), ethaboxam, was already described as afungicidal compound for crop protection in Korean Patent No. 124,552(Korean patent application No. 94-19960). Further, ethaboxam-containingformulations, e.g. wettable powder (trade name: Guardian; marketed byMisung Ltd.) were known.

[0004] An adjuvant is a non-pesticidal compound for enhancing a totalactivity of a pesticide, differently from a co-formulant which controlsphysical properties of active ingredients to facilitate their handling.Presence of the adjuvant in a pesticidal formulation increases a totalquantity of active ingredients which can be contacted with and/orpenetrated into a target plant thereby to enhance the activity ofpesticide and to remarkably reduce the quantity of active ingredientswhich needs to be applied. Currently, Environmental Protection Agency inthe U.S.A. and Ministry of Agriculture, Fisheries and Food in the UnitedKingdom are recognizing the employment of the adjuvant as a major toolfor obtaining desired activity of novel active ingredients.

[0005] An adjuvant is widely used in leading advanced countries such asthe U.S.A. and European countries and conventionally, is manufacturedand marketed as a separate package for use as a tank-mix formulation inspraying herbicides. Recently, its application is also extended tofungicides, insecticides, growth regulators and fertilizers. However,the adjuvant for use as the tank-mix formulation is manufactured as aseparate package and thus, its production and transportation costs areunavoidably increased and particularly, strict experimental data arerequired for its registration. Therefore, its development takes a longtime and requires enormous expenses.

[0006] Recently, several leading agrochemical manufacturers are likelyto formulate an adjuvant in combination with active ingredients in onepackage thereby to facilitate mixing, transportation and particularly,registration of products. A formulation containing the adjuvant incombination with the active ingredients in one package is referred to asa premixed one-pack formulation, a contrary concept to a tank-mixedformulation. An example of the premixed one-pack formulations is around-up formulation containing as the adjuvant tallow amine and as theherbicidal compound glyphosate in one package.

[0007] Conventionally, an adjuvant for fungicides is added to a sprayliquid when applied and a product containing 75-95% of a mineral oil and5-25% of a surfactant is widely used. This adjuvant increases thefungicidal activity by improving the retention of active ingredients toplants rather than by increasing foliar penetration of activeingredients. However, such mineral oil-containing product may causeinjury to plants and environmental contamination due to its lowbiodegradability.

[0008] Recently, in order to increase the efficacy of high-activitypenetrative fungicides, it was suggested that non-ionic surfactants suchas sorbitan esters of fatty acids, polyoxyethylene alkyl ethers,polyoxyethylene sorbitan esters, polyoxyethylene alkyl phenol ethers,polyoxyethylene amides be incorporated into the fungicides (see U.S.Pat. No. 5,905,072). Examples of fungicides which can be employed are asfollows: triazoles, e.g. tetraconazole, triadimefon, triadimenol,propiconazole, penconazole, hexaconazole, cyproconazole, flusilazole,etc.; imidazoles, e.g. prochloraz, imazalil, etc.; morpholines, e.g.fenpropimorph, tridemorph etc.; dicarboxyimides, e.g. iprodione,vinclozolin, etc.; piperidines, e.g. fenprodipin, etc.; acyl alanines,e.g. metalaxyl, benalaxyl, etc. In particular, it was disclosed thatpolyoxyethylene alkyl ethers selectively enhance the efficacy of thepenetrative fungicide, benzyl triazolyl cyclopentanes (see U.S. Pat. No.5,393,770).

[0009] Accordingly, in order to enhance the fungicidal activity ofethaboxam and to reduce the quantity thereof which needs to be applied,screening of an environment friendly adjuvant and development of a novelfungicidal composition using the same may provide many advantages inboth commercial and environmental aspects.

DISCLOSURE OF THE INVENTION

[0010] In order to develop a compound enhancing the efficacy ofethaboxam and reducing its quantity which needs to be applied, thepresent inventors incorporated various potential compounds includinganionic and nonionic surfactants into ethaboxam, and conductedexperiments for their efficacy enhancement activity. As a result, theyfound that nonionic surfactants of polyoxyalkylene alkyl ether classcause enhancement of activity. Thus, they prepared a one-packformulation containing them, and found that such formulation remarkablyenhances the fungicidal activity at a given level of ethaboxam. Further,they found that the formulation containing a particular polyoxyalkylenealkyl ether has equivalent or superior efficacy even at a half or lesslevel of ethaboxam, as compared with polyoxyalkylene alkyl ether-freeethaboxam formulation and thus, completed the present invention.

[0011] Thus, it is an object of the present invention to provide afungicidal composition comprising ethaboxam and a non-pesticidaladjuvant which is more cost-effective and readily biodegradable thanactive ingredients.

[0012] A first aspect of the present invention provides a fungicidalcomposition which comprisesN-(α-cyano-2-thenyl)-4-ethyl-2-(ethylamino)-5-thiazolecarboxaramide ofthe formula:

[0013] (hereinafter, referred to as ethaboxam) and a nonionicsurfactant.

[0014] A further aspect of the present invention provides a method forenhancing the activity of ethaboxam, which comprises adding a nonionicsurfactant to ethaboxam formulation.

[0015] A still further aspect of the present invention provides a methodfor controlling undesired phytopathogens which comprises applying aformulation prepared from the composition of the present invention totarget plants.

[0016] The nonionic surfactant which can be employed in the presentinvention is classified into polyoxyalkylene alkyl ether havingpolyoxyalkylene as the hydrophilic moiety and aliphatic alcohol as thelipophilic moiety. Preferred polyoxyalkylene alkyl ether is derived fromsaturated or unsaturated alcohol having the alkyl chain of 12 to 18carbon atoms or mixtures thereof More preferred polyoxyalkylene alkylether is derived from lauryl alcohol having 12 carbon atoms, cetylalcohol having 16 carbon atoms, stearyl alcohol being saturated andhaving 18 carbon atoms or oleyl alcohol being unsaturated and having 18carbon atoms. In the present invention, polyoxyethylene isrepresentative polyoxyalkylene, but polyoxyethylene-polyoxypropylenecopolymer wherein ethylene oxide and propylene oxide is copolymerized isalso included. For example, polyoxyethylene has an average of 3 to 50,more preferably, 7 to 20, most preferably, 10 to 14 ethylene oxide unitsper molecule, depending upon the number of carbon atoms in the alkylchain derived from aliphatic alcohol. In the present invention,particularly preferred is polyoxyethylene lauryl ether, polyoxyethylenecetyl ether, polyoxyethylene stearyl ether or polyoxyethylene oleylether, each of which has an average of 7 to 20 ethylene oxide units permolecule. Polyoxyalkylene alkyl ether employed in the present inventionmay be obtained by copolymerization of ethylene oxide and natural orsynthetic aliphatic alcohol having 12 to 18 carbon atoms and the purityof 50 to 98%.

[0017] The fungicidal composition of the present invention contains 1 to8 wt %, preferably, 5 to 50 wt % of ethaboxam, 10 to 50 wt % ofadjuvant, 10 to 89 wt % of solid or liquid carrier or additive and 0 to20 wt %, preferably, 0.1 to 10 wt % of surfactants. In case where thecomposition contains less than 1 wt % of ethaboxam, it is difficult tocontrol the dilution fold. By contrast, in case where the compositioncontains more than 80 wt % of ethaboxam, it is difficult to maintainphysical properties of formulations.

[0018] In the composition of the present invention, the presence ofpolyoxyalkylene alkyl ether reduces the quantity of ethaboxam whichneeds to be applied to obtain a given level of activity to a significantextent. Practically, a concentration of ethaboxam in a spray forcontrolling downy mildew is approximately 250 mg/l. But in case ofcontaining 100 to 2000 mg/l of a particular polyoxyalkylene alkyl etherin a premixed one-pack or tank-mixed formulation, even at a half or lessconcentration of ethaboxam, the efficacy is equivalent or superior tothat of the polyoxyalkylene alkyl ether-free formulation.

[0019] In the composition for one-pack formulation, an adjuvant iscomprised at 10 to 50% by weight. Enhancement of activity can beobtained not only in a one-pack formulation but also in a tank-mixedformulation. But, the concentration of the adjuvant is not fixed in thetank-mixed formulation, differently in the one-pack formulation. It issuggested that enhancement of the activity by addition of adjuvantresults from the increase of the permeability into plants by improvementof foliar penetration. This can be inferred from the differences inpermeability according to the concentration of adjuvant.

[0020] In the present invention, a weight ratio of ethaboxam to adjuvantranges from about 1:0.5 to about 1:10, preferably, from about 1:1 toabout 1:5.

[0021] The fungicidal composition in accordance with the presentinvention is effective for preventing or curing plant diseases caused byphytopathogens as follows: gerbera phytophthora root rot (Phytophthoracryptogea), potato late blight (Phytophthora infestans), hot pepperphytophthora blight (Phytophthora capsici), tomato late blight(Phytophthora infestans), tobacco black shank (Phytophthora nicotianaevar. nicotinae), sesame rot (Phytophthora nicotianae var. parasitica),apple phytophthora fruit rot (Phytophthora cactorum), Cucumis melo L.var. makuwa MAKINO downy mildew (Pseudoperonospora cubensis), melondowny mildew (Pseudoperonospora cubensis), cucumber downy mildew(Pseudoperonospora cubensis), cabbage downy mildew (Peronosporaparasitica), lettuce downy mildew (Bremia lactucae), rose downy mildew(Peronospora sparsa), grape downy mildew (Plasmopara viticola), hopdowny mildew (Pseudoperonospora humuli) and turf grass Pythium blight(Phythium spp.)

[0022] If desired, the fungicidal composition of the present inventioncontains carriers, surfactants or co-formulants conveniently used in thepesticide formulation area. For example, the composition is processed tounreformed forms,-for example, to formulations such as wettable powderprepared by homogeneously mixing active ingredient with extender (e.g.solvent, solid carriers and if appropriate, surfactants) and/or grindingthe mixture, dispersible concentrate, emulsifiable concentrate, waterdispersible granule, suspension concentrate, oil flowable, etc. andapplied by spraying onto foliage and stems of plants. Applicationfrequency and application rate are varied depending on biologicalproperties of pathogens and weather environment. Suitable carrier andadditive may be solid or liquid which is generally used in the pesticideformulation, for example, natural or synthetic inorganic materials,solvent, dispersing agents, wetting agents, diluents and the like.Employable solvent is polar solvent such as N-methyl-2-pyrrolidone,dimethyl sulfoxide or dimethyl formamide. Auxiliary solvent islong-chain alcohol such as N-octyl-2-pyrrolidone, substitutednaphthalene, xylene, substituted benzene, decyl alcohol, dodecylalcohol, etc. and long-chain ester compounds. Employable solid carrieris micronized natural mineral such as talc, kaolin, calcium carbonate,diatomite or pyrophyllite. Moreover, to improve physical properties,particularly wettability, of. formulation, a water-soluble ioniccompound such as anhydrous sodium sulfate or hydrophilic poroussynthetic compound may be employed.

[0023] An adjuvant may be adsorbed with an adsorbent such ashigh-dispersible synthetic silica or high-dispersible adsorbing polymer,etc. (e.g. white carbon, synthetic calcium silicate) within the range ofhaving no harmful effects on storage stability, particularly, at aweight ratio of the adjuvant to the adsorbent ranging from 2:1 to 1:1.Surfactants having various properties may be used depending upon thetype of ethaboxam formulations, but suitable is nonionic or anionicsurfactant having good wettability and dispersibility. As used herein,surfactants include mixtures thereof A wetting agent employable in thepresent invention includes anionic wetting agent such as sodium laurylsulfate, polyoxyalkylene alkyl phenyl ether sulfonate, dialkylsulfosuccinate, dialkyl naphthalene sulfonate, polyoxyalkylene alkylether sulfate, etc., nonionic wetting agent such as acetylene classesand urea complex of non-ionic surfactant. More preferred is sodiumlauryl sulfate, polyoxyalkylene alkyl phenyl ether sulfonate,polyoxyalkylene alkyl ether sulfate or urea complex of nonionicsurfactant, etc.

[0024] In powder formulations, dispersing agent includes anionicdispersing agent such as lignin sulfonate, naphthalene sulfonate, laurylsulfate, lauryl sulfonate, polyoxyalkylene alkyl aryl ether sulfate,polyoxyalkylene alkyl ether sulfate, etc. and nonionic dispersing agentsuch as polyoxyalkylene alkyl aryl ether, polyoxyalkylene alkyl ether,etc. However, in case of using polyoxyethylene cetyl ether orpolyoxyethylene stearyl ether with an average of 10 or more ethyleneoxide units per molecule as adjuvant, additional dispersing agent maynot be comprised because the adjuvant may also function as thedispersing agent. In liquid formulations, dispersing agent such asnonionic dispersing agent with a high dispersibility, for example,polyoxyalkylene alkyl aryl ether, preferably, polyoxyalkylene tristyrylphenol ether or polyoxyalkylene alkyl ether, etc. may be used. In manycases, such dispersing agent is also useful as wetting agent. Wettingand dispersing agents are not limited to those as mentioned above, andmay be selected among suitable nonionic or anionic surfactants.

[0025] The fungicidal composition of the present invention may bemanufactured into premixed one-pack formulations by mixing ethaboxam andadjuvant with carrier or surfactant or tank-mixed formulations. In thiscase, -the concentrations of ethaboxam and adjuvant are adjusted toabout 30 to about 300 mg/l and about 100 to 2000 mg/l, respectively.

[0026] The composition according to the present invention may furthercomprise one or more additional agents for preventing or curing plantdiseases, which include, but are not limited to, azoxystrobin, copperoxychloride, cymoxanil, dimethomorph, famoxadone, fluazinam metalaxyl,oxadixyl, chlorothalonil, dithianon, folfet, mancozeb, propineb, etc.

[0027] In the present invention, wettable powder may be prepared by thefollowing procedure: ethaboxam is mixed with co-formulants other thanadjuvant and absorbent and the mixture is ground using a suitable mill.Adjuvant is previously adsorbed to adsorbent such as white carbon, etc.and ground by Warning blender. Then, the two ground parts arehomogeneously mixed to obtain the fungicidal composition. On the otherhand, dispersible concentrate may be prepared by the followingprocedure: active ingredient, adjuvant and other co-formulants aredissolved using a suitable mixer to obtain the homogeneous combination.

BEST MODE FOR CARRYING OUT THE INVENTION

[0028] Hereinafter, the present invention will be explained in moredetail with reference to the following examples. However, these examplesare merely illustrative of, and are not intended to, nor should beintended to, limit the present invention.

[0029] Formulations having the compositions as set forth in thefollowing tables were prepared. Unless specifically indicated, nrepresents an average of ethylene oxide units per molecule. In thetables, KONION and Brij represent products by Korea Polyol (Korea) andUniQema (UK), respectively and Koremul and HY by Han Nong Chemicals(Korea).

EXAMPLES 1 to 5 Preparation of Wettable Powder

[0030] Polyoxyethylene alkyl ether was previously adsorbed to whitecarbon and ground by Warning blender. Ethaboxam was homogeneously mixedwith other co-formulants using a vinyl bag and then, the mixture wasground in a mill. Then, the two ground parts were homogeneously mixed toobtain the wettable powder (Table 1). TABLE 1 Example 1 2 3 4 5Ethaboxam 12.5 12.5 12.5 12.5 12.5 Polyoxyethylene(n = 10) lauryl ether40 — — — — (KONION LA-10) Polyoxyethylene(n = 20) lauryl ether — 40 — —— (KONION LA-20) Polyoxyethylene(n = 10) cetyl ether — — 40 — — (Brij56) Polyoxyethylene(n = 12) cetyl ether — — — 40 — (Koremul CE-12)Polyoxyethylene(n = 20) cetyl ether — — — — 40 (Brij 58) Anhydroussodium sulfate 15.5 15.5 15.5 15.5 15.5 Sodium lauryl sulfate 2 2 2 2 2Sodium lignin sulfonate 3 3 3 3 3 White carbon(Zeosil 39) 27.0 27.0 27.027.0 27.0

EXAMPLES 6 to 10 Preparation of Wettable Powder

[0031] Wettable powder having the composition as set forth in Table 2was prepared according to the substantially same procedure as Examples 1to 5. TABLE 2 Example 6 7 8 9 10 Ethaboxam 12.5 12.5 12.5 12.5 12.5Polyoxyethylene(n = 15) oleyl ether 40 — — — — (KONION OA-15)Polyoxyethylene(n = 20) oleyl ether — 40 — — — (Koremul OE-20)Polyoxyethylene(n = 10) stearyl ether — — 40 — — (Brij 76)Polyoxyethylene(n = 14) stearyl ether — — — 40 — (Koremul SE-14)Polyoxyethylene(n = 20) stearyl ether — — — — 40 (Brij 78) Anhydroussodium sulfate 15.5 15.5 15.5 15.5 15.5 Sodium lauryl sulfate 2 2 2 2 2Sodium lignin sulfonate 3 3 3 3 3 White carbon(Zeosil 39) 27.0 27.0 27.027.0 27.0

EXAMPLES 11 to 13 Preparation of Wettable Powder

[0032] Wettable powder having the composition as set forth in Table 3was prepared according to the substantially same procedure as Examples 1to 5. TABLE 3 Example 11 12 13 Ethaboxam 12.5 12.5 12.5Polyoxyethylene(n = 12) cetyl 12.5 25.0 37.5 ether(Koremul CE-12)Anhydrous sodium sulfate 15.5 15.5 15.5 Sodium lauryl sulfate 2 2 2Sodium lignin sulfonate 3 3 3 White carbon(Zeosil 39) 27 27 27 Kaolin27.5 15 2.5

EXAMPLES 14 to 16 Preparation of Dispersible Concentrate

[0033] Ethaboxam was previously dissolved in N-methyl-2-pyrrolidone towhich were added other co-formulants and adjuvant and dissolved toobtain the dispersible concentrate(Table 4). TABLE 4 Example 14 15 16Ethaboxam 12.5 12.5 12.5 Polyoxyethylene(n = 7) lauryl 25 — —ether(KONION LA-7) Polyoxyethylene(n = 10) lauryl — 25 — ether(KONIONLA-10) Polyoxyethylene(n = 20) lauryl — — 25 ether(KONION LA-20)Polyoxyethylene tristyryl 5 5 5 phenyl ether(HY-310F)N-methyl-2-pyrrolidone 57.5 57.5 57.5

EXAMPLES 17 to 20 Preparation of Dispersible Concentrate

[0034] Dispersible concentrate having the composition as set forth inTable 5 was prepared according to the substantially same procedure asExamples 14 to 16. TABLE 5 Example 17 18 19 20 Ethaboxam 12.5 12.5 12.512.5 Polyoxyethylene(n = 7) cetyl 25 — — — ether(Koremul CE-7)Polyoxyethylene(n = 10) cetyl — 25 — — ether(Brij 56) Polyoxyethylene(n= 15) cetyl — — 25 — ether(Koremul CE-12) Polyoxyethylene(n = 20) cetyl— — — 25 ether(Brij 58) Polyoxyethylene tristyryl 5 5 5 5 phenyl ether(HY-310F) N-methyl-2-pyrrolidone 57.5 57.5 57.5 57.5

EXAMPLES 21 to 24 Preparation of Dispersible Concentrate

[0035] Dispersible concentrate having the composition as set forth inTable 6 was prepared according to the substantially same procedure asExamples 14 to 16. TABLE 6 Example 21 22 23 24 Ethaboxam 12.5 12.5 12.512.5 Polyoxyethylene(n = 7) oleyl 25 — — — ether(Koremul OE-7)Polyoxyethylene(n = 10) oleyl — 25 — — ether(Koremul OE-10)Polyoxyethylene(n = 15) oleyl — — 25 — ether(KONION OA-15)Polyoxyethylene(n = 20) oleyl — — — 25 ether(Koremul OE-20)Polyoxyethylene tristyryl 5 5 5 5 phenyl ether(HY-310F)N-methyl-2-pyrrolidone 57.5 57.5 57.5 57.5

EXAMPLES 25 to 28 Preparation of Dispersible Concentrate

[0036] Dispersible concentrate having the composition as set forth inTable 7 was prepared according to the substantially same procedure asExamples 14 to 16. TABLE 7 Example 25 26 27 28 Ethaboxam 12.5 12.5 12.512.5 Polyoxyethylene(n = 7) stearyl 25 — — — ether(Koremul SE-7)Polyoxyethylene(n = 10) stearyl — 25 — — ether(Brij 76)Polyoxyethylene(n = 14) stearyl — — 25 — ether(Koremul SE-14)Polyoxyethylene(n = 20) stearyl — — — 25 ether(Brij 78) Polyoxyethylenetristyryl 5 5 5 5 phenyl ether(HY-310F) N-methyl-2-pyrrolidone 57.5 57.557.5 57.5

EXAMPLES 29 to 31 Preparation of Dispersible Concentrate

[0037] Dispersible concentrate having the composition as set forth inTable 8 was prepared according to the substantially same procedure asExamples 14 to 16. TABLE 8 Example 29 30 31 Ethaboxam 8.5 8.5 8.5Polyoxyethylene(n = 12) cetyl 17.0 25.5 34.0 ether(Koremul CE-12)Polyoxyethylene tristyryl 10 10 10 phenyl ether(HY-310F)N-methyl-2-pyrrolidone 64.5 56.0 47.5

EXAMPLES 32 to 36 Preparation of Wettable Powder

[0038] Wettable powder having the composition as set forth in Table 9was prepared according to the substantially same procedure as Examples 1to 5. TABLE 9 Example 32 33 34 35 36 Ethaboxam 7 7 7 7 7 Azoxystrobin¹⁾5 — — — — Copper oxychloride²⁾ — 30 — — — Cymoxanil³⁾ — — 6 — —Dimethomorph⁴⁾ — — — 15 — Famoxadone⁵⁾ — — — — 9 Polyoxyethylene(n = 12)40 30 40 40 40 cetyl ether(Koremul CE-12) Sodium lauryl sulfate 2 2 2 22 White carbon(Zeosil 39) 26.7 20 26.7 26.7 26.7 Anhydrous sodiumsulfate 19.3 11 18.3 9.3 15.3

EXAMPLES 37 to 39 Preparation of Wettable Powder

[0039] Wettable powder having the composition as set forth in Table 10was prepared according to the substantially same procedure as Examples 1to 5. TABLE 10 Example 37 38 39 Ethaboxam 7 7 7 Fluazinam¹⁾ 12.5 — —Metalaxyl²⁾ — 12.5 — Oxadixyl³⁾ — — 16 Polyoxyethylene(n = 12) cetyl 4040 40 ether(Koremul CE-12) Sodium lauryl sulfate 2 2 2 Whitecarbon(Zeosil 39) 26.7 26.7 26.7 Anhydrous sodium sulfate 11.8 11.8 8.3

EXAMPLES 40 to 44 Preparation of Wettable Powder

[0040] Wettable powder having the composition as set forth in Table 11was prepared according to the substantially same procedure as Examples 1to 5. TABLE 11 Example 40 41 42 43 44 Ethaboxam 3.5 3.5 3.5 3.5 3.5Chlorothalonil¹⁾ 60 — — — — Dithianone²⁾ — 30 — — — Folfet³⁾ — — 20 — —Mancozeb⁴⁾ — — — 50 — Propineb⁵⁾ — — — — 50 Polyoxyethylene(n = 12) 1530 30 15 15 cetyl ether(Koremul CE-12) Sodium lauryl sulfate 2 2 2 2 2White carbon(Zeosil 39) 10 20 10 10 10 Anhydrous Sodium sulfate 9.5 14.524.5 19.5 19.5

COMPARATIVE EXAMPLES 1 and 2 Preparation of Dispersible Concentrate

[0041] Ethaboxam co-formulants and extenders were introduced into avinyl bag and homogeneously mixed. Then, the mixture was ground toobtain the wettable powder(Table 12). TABLE 12 Comparative Example 1 2Ethaboxam 12.5 25.0 Anhydrous sodium sulfate 15.5 15.5 Sodium laurylsulfate 2 2 Sodium lignin sulfonate 3 3 White carbon(Zeosil 39) 27 27Kaolin 40 27.5

COMPARATIVE EXAMPLES 3 to 5 Preparation of Dispersible Concentrate

[0042] Ethaboxam was previously dissolved in N-methyl-2-pyrrolidone andother co-formulants and adjuvant were added thereto and dissolved toobtain the dispersible concentrate(Table 13). TABLE 13 ComparativeExample 3 4 5 Ethaboxam 12.5 8.5 8.5 Polyoxyethylene(n = 12) cetyl — —8.5 ether(Koremul CE-12) Polyoxyethylene tristyryl 5 10 10 phenylether(HY-310F) Polyoxyethylene(n = 20) sorbitan 25 — — monolaurate(Tween20) N-methyl-2-pyrrolidone 57.5 81.5 73.0

Evaluation of biological activity

[0043] Enhancement of efficacy by the presence of polyoxyalkylene alkylether can be supported by the increase of efficacy of the fungicidalcomposition containing a particular polyoxyalkylene alkyl ether, ascompared with that of polyoxyalkylene alkyl ether-free composition. Inaddition, enhancement of efficacy by combined formulation can besupported by the maintenance or the increase of efficacy of combinedformulation further containing other agents for controlling plantdiseases, as compared with that of single formulation having arelatively higher concentration of ethaboxam.

EXPERIMENT 1 Activity of Premixed One-Pack Formulations ContainingEthaboxam and Polyoxyalkylene Alkyl Ether

[0044] 1) Activity on Tomato Late Blight(Phytophthora infestans)

[0045] A) Preventive Activity

[0046] Tomato seeds were sown in a horticultural bed soil of pots havinga diameter of 6 cm and grown under glass for 4 weeks. Spray liquidshaving the concentrations of 1, 5, 10, 50 and 100 mg/l as activeingredients, respectively, were prepared from the wettable powder andthe dispersible concentrate. The spray liquids were sprayed onto tomatoleaves and stems at 5 ml per pot using an atomizer and dried in agreenhouse for 24 hours. Phytophthora infestans was prepared at aconcentration of 1×10⁴ zoospores/ml and inoculated into the plants usingan atomizer. In order to induce the disease, the inoculated plants wereplaced at 20° C. under the relative humidity of 100% for 3 to 4 days.When the incidence rate of disease in the untreated group reached 80% ormore, the incidence rate of disease in each group was measured. Theresults are shown in the following Tables 14 and 15. TABLE 14 Percentageof infected area(%) Concentration as active ingredient(mg/l) Formulation1 5 10 50 100 Example 1 10 6 2 0 0 Example 2 10 7 2 0 0 Example 3 1 1 00 0 Example 4 0 0 0 0 0 Example 5 1 1 0 0 0 Example 6 5 5 1 0 0 Example7 5 3 1 0 0 Example 8 2 2 1 0 0 Example 9 1 2 0 0 0 Example 10 2 2 1 0 0Comparative 20 13 5 0 0 Example 1 Comparative 21 11 5 0 0 Example 2Guardian 15 5 3 0 0 Wettable Powder¹⁾ Untreated 95

[0047] TABLE 15 Percentage of infected area(%) Concentration as activeingredient(mg/l) Formulation 1 5 10 50 100 Example 14 10 4 2 0 0 Example15 9 3 3 0 0 Example 16 8 4 3 0 0 Example 17 2 1 0 0 0 Example 18 2 1 00 0 Example 19 1 1 0 0 0 Example 20 1 1 0 0 0 Example 21 7 3 1 0 0Example 22 7 2 2 0 0 Example 23 6 3 2 0 0 Example 24 4 3 2 0 0 Example25 2 2 0 0 0 Example 26 1 2 1 0 0 Example 27 1 1 0 0 0 Example 28 1 1 00 0 Comparative 12 6 3 0 0 Example 3 Guardian 15 5 3 0 0 WettablePowder¹⁾ Untreated 95

[0048] As shown in the above tables, the formulations containingpolyoxyalkylene alkyl ether considerably enhanced the efficacy, ascompared with polyoxyalkylene alkyl ether-free formulations. Especially,the formulations containing polyoxyethylene cetyl ether had theoutstanding effect, that is, superior efficacy to Guardian(Misung Ltd.)even at a half or less concentration of ethaboxam.

[0049] B) Curative Activity

[0050] Tomato seeds were sown in a horticultural bed soil of pots havinga diameter of 6 cm and grown under glass for 4 weeks. Phytophthorainfestans was prepared at a concentration of 1×10⁴ zoospores/ml andinoculated into the plants using an atomizer. In order to induce thedisease, the inoculated plants were placed at 20° C. under the relativehumidity of 100% for 24 hours. Spray liquids having the concentrationsof 1, 5, 10, 50 and 100 mg/l as active ingredient, respectively, wereprepared from the wettable powder and the dispersible concentrate. Thespray liquids were sprayed onto tomato leaves and stems at 5 ml per potusing an atomizer and then, the disease was induced at 20° C. under therelative humidity of 100% for 2 to 3 days. When the incidence rate ofdisease in the untreated group reached 80% or more, the incidence rateof disease in each group was measured. The results are shown in thefollowing Tables 16 and 17. TABLE 16 Percentage of infected area(%)Concentration as active ingredient(mg/l) Formulation 1 5 10 50 100Example 1 17 9 5 0 0 Example 2 19 11 7 0 0 Example 3 4 2 1 0 0 Example 43 2 0 0 0 Example 5 3 1 0 0 0 Example 6 9 7 3 0 0 Example 7 10 6 2 0 0Example 8 4 3 1 0 0 Example 9 5 2 2 0 0 Example 10 5 2 1 0 0 Comparative40 17 13 1 0 Example 1 Comparative 37 15 12 1 0 Example 2 Guardian 35 1510 1 0 Wettable Powder¹⁾ Untreated 100

[0051] TABLE 17 Percentage of infected area(%) Concentration as activeingredient(mg/l) Formulation 1 5 10 50 100 Example 14 15 8 5 0 0 Example15 12 7 5 0 0 Example 16 10 7 7 0 0 Example 17 2 1 1 0 0 Example 18 3 11 0 0 Example 19 1 0 0 0 0 Example 20 3 1 0 0 0 Example 21 7 6 3 0 0Example 22 8 3 3 0 0 Example 23 7 3 2 0 0 Example 24 7 4 3 0 0 Example25 3 1 0 0 0 Example 26 2 1 1 0 0 Example 27 2 0 0 0 0 Example 28 1 1 10 0 Comparative 20 11 8 1 0 Example 3 Guardian 35 15 10 1 0 WettablePowder¹⁾ Untreated 100

[0052] As shown in the above tables, the curative activity of tomatolate blight was significantly enhanced as compared with the comparativeexample and Guardian wettable powder where polyoxyalkylene alkyl etherwas not contained. It had a similar pattern to the preventive activitythereof Accordingly, it was confirmed that the fungicidal composition ofthe present invention enhanced both preventive and curative activitiesof tomato late blight.

[0053] 2) Activity on Potato Late Blight (Phytophthora infestans)

[0054] A) Preventive Activity

[0055] Artificial seed potatoes were sown in a horticultural bed soil ofpots having a diameter of 6 cm and grown under glass for 4 weeks. Sprayliquids having the concentrations of 1, 5, 10, 50 and 100 mg/l as activeingredient, respectively, were prepared from the wettable powder and thedispersible concentrate. The spray liquids were sprayed onto potatoleaves and stems at 5 ml per pot using an atomizer and dried in agreenhouse for 24 hours. Phytophthora infestans was prepared at aconcentration of 1×10⁴ zoospores/ml and inoculated into the plants usingan atomizer. In order to induce 5 the disease, the inoculated plantswere placed at 20° C. under the relative humidity of 100% for 3 to 4days. When the incidence rate of disease in the untreated group reached80% or more, the incidence rate of disease in each group was measured.The results are shown in the following Tables 18 and 19. TABLE 18Percentage of infected area(%) Concentration as active ingredient(mg/l)Formulation 1 5 10 50 100 Example 1 12 10 7 0 0 Example 2 13 10 7 0 0Example 3 3 2 1 0 0 Example 4 3 1 0 0 0 Example 5 4 3 1 0 0 Example 6 97 5 0 0 Example 7 10 7 6 0 0 Example 8 4 3 1 0 0 Example 9 4 2 0 0 0Example 10 3 3 1 0 0 Comparative 25 20 10 0 0 Example 1 Comparative 2321 10 0 0 Example 2 Guardian Wettable Powder¹⁾ 20 13 8 0 0 Untreated 100

[0056] TABLE 19 Percentage of infected area(%) Concentration as activeingredient(mg/l) Formulation 1 5 10 50 100 Example 14 10 8 7 0 0 Example15 12 8 5 0 0 Example 16 10 7 4 0 0 Example 17 2 1 1 0 0 Example 18 3 11 0 0 Example 19 2 1 0 0 0 Example 20 3 1 0 0 0 Example 21 7 3 3 0 0Example 22 8 4 2 0 0 Example 23 9 3 1 0 0 Example 24 7 7 3 0 0 Example25 3 2 1 0 0 Example 26 2 1 0 0 0 Example 27 2 1 1 0 0 Example 28 2 2 20 0 Comparative 17 14 10 0 0 Example 3 Guardian 20 13 8 0 0 WettablePowder¹⁾ Untreated 100

[0057] As shown in the above tables, the preventive activity of potatolate blight was similar to that of tomato late blight.

[0058] B) Curative Activity

[0059] Artificial seed potatoes were sown in a horticultural bed soil ofpots having a diameter of 6 cm and grown under glass for 4 weeks.Phytophthora infestans was prepared at a concentration of 1×10⁴zoospores/ml and inoculated into the plants using an atomizer. In orderto induce the disease, the inoculated plants were placed at 20° C. underthe relative humidity of 100% for 24 hours. Spray liquids having theconcentrations of 1, 5, 10, 50 and 100 mg/l as active ingredient,respectively, were prepared from the wettable powder and the dispersibleconcentrate. The spray liquids were sprayed onto potato leaves and stemsat 5 ml per pot using an atomizer and then, the disease was induced at20° C. under the relative humidity of 100% for 2 to 3 days. When theincidence rate of disease in the untreated group reached 80% or more,the incidence rate of disease in each group was measured. The resultsare shown in the following Tables 20 and 21. TABLE 20 Percentage ofinfected area(%) Concentration as active ingredient(mg/l) Formulation 15 10 50 100 Example 1 16 11 6 0 0 Example 2 16 13 7 0 0 Example 3 5 2 10 0 Example 4 3 2 1 0 0 Example 5 3 3 1 0 0 Example 6 10 7 4 0 0 Example7 14 9 2 0 0 Example 8 4 3 1 0 0 Example 9 3 3 2 0 0 Example 10 5 3 1 00 Comparative 38 17 13 1 0 Example 1 Comparative 35 16 13 1 0 Example 2Guardian 40 17 15 3 0 Wettable Powder¹⁾ Untreated 100

[0060] TABLE 21 Percentage of infected area(%) Concentration as activeingredient(mg/l) Formulation 1 5 10 50 100 Example 14 17 13 7 0 0Example 15 15 12 5 0 0 Example 16 13 12 5 0 0 Example 17 4 3 0 0 0Example 18 5 2 1 0 0 Example 19 3 1 0 0 0 Example 20 5 2 1 0 0 Example21 11 8 5 0 0 Example 22 10 7 4 0 0 Example 23 9 7 5 0 0 Example 24 13 85 0 0 Example 25 5 4 2 0 0 Example 26 5 3 2 0 0 Example 27 4 3 1 0 0Example 28 6 2 1 0 0 Comparative 30 12 10 1 0 Example 3 Guardian 40 1715 3 0 Wettable Powder¹⁾ Untreated 100

[0061] As shown in the above tables, the curative activity of potatolate blight was also similar to that of tomato late blight. Accordingly,it was confirmed that the fungicidal composition of the presentinvention enhanced both preventive and curative activities of potatolate blight.

[0062] 3) Activity on Cucumber Downy Mildew (Pseudoperonospora cubensis)

[0063] A) Preventive Activity

[0064] Cucumber seeds were sown in a horticultural bed soil of potshaving a diameter of 6 cm and grown under glass for 4 weeks. Sprayliquids having the concentrations of 1, 5, 10, 50 and 100 mg/l as activeingredient, respectively, were prepared from the wettable powder and thedispersible concentrate. The spray liquids were sprayed onto cucumberleaves and stems at 5 ml per pot using an atomizer and dried in agreenhouse for 24 hours. Pseudoperonospora cubensis was prepared at aconcentration of 5×10⁴ zoosporangia/ml and inoculated into the plantsusing an atomizer. In order to induce the disease, the inoculated plantswere placed at 20° C. under the relative humidity of 100% for 3 to 4days. When the incidence rate of disease in the untreated group reached80% or more, the incidence rate of disease in each group was measured:The results are shown in the following Tables 22 and 23. TABLE 22Percentage of infected area(%) Concentration as active ingredient(mg/l)Formulation 1 5 10 50 100 Example 1 7 4 4 0 0 Example 2 6 6 3 0 0Example 3 2 1 0 0 0 Example 4 1 1 0 0 0 Example 5 1 1 0 0 0 Example 6 55 2 0 0 Example 7 4 3 2 0 0 Example 8 2 2 1 0 0 Example 9 1 1 0 0 0Example 10 2 1 1 0 0 Comparative Example 1 16 10 7 0 0 ComparativeExample 2 15 10 7 0 0 Guardian Wettable Powder¹⁾ 13 8 6 0 0 Untreated 80

[0065] TABLE 23 Percentage of infected area(%) Concentration as activeingredient(mg/l) Formulation 1 5 10 50 100 Example 14 8 8 6 0 0 Example15 10 7 6 0 0 Example 16 9 6 5 0 0 Example 17 3 2 0 0 0 Example 18 2 2 00 0 Example 19 2 1 0 0 0 Example 20 2 2 0 0 0 Example 21 8 7 4 0 0Example 22 7 5 3 0 0 Example 23 7 5 1 0 0 Example 24 9 6 3 0 0 Example25 4 3 1 0 0 Example 26 2 2 1 0 0 Example 27 2 2 2 0 0 Example 28 3 3 00 0 Comparative 14 10 8 0 0 Example 3 Guardian 13 6 6 0 0 WettablePowder¹⁾ Untreated 80

[0066] As shown in the above tables, in the untreated group, theincidence rate of cucumber downy mildew was slightly lower than tomatoand potato late blights because of its characteristics, but thepreventive activity of cucumber downy mildew was similar to that oftomato and potato late blights.

[0067] B) Curative Activity

[0068] Cucumber seeds were sown in a horticultural bed soil of potshaving a diameter of 6 cm and grown under glass for 4 weeks.Pseudoperonospora cubensis was prepared at a concentration of 5×10⁴zoosporangia/ml and inoculated into the plants using an atomizer. Inorder to induce the disease, the inoculated plants were placed at 20° C.under the relative humidity of 100% for 24 hours. Spray liquids havingthe concentrations of 1, 5, 10, 50 and 100 mg/l as active ingredient,respectively, were prepared from the wettable powder and the dispersibleconcentrate. The spray liquids were sprayed onto cucumber leaves andstems at 5 ml per pot using an atomizer and then, the disease wasinduced at 20° C. under the relative humidity of 100% for 2 to 3 days.When the incidence rate of disease in the untreated group reached 80% ormore, the incidence rate of disease in each group was measured. Theresults are shown in the following Tables 24 and 25. TABLE 24 Percentageof infected area(%) Concentration as active ingredient(mg/l) Formulation1 5 10 50 100 Example 1 13 10 5 0 0 Example 2 12 8 5 0 0 Example 3 5 2 10 0 Example 4 2 1 1 0 0 Example 5 4 2 0 0 0 Example 6 8 7 5 0 0 Example7 10 7 6 0 0 Example 8 4 2 0 0 0 Example 9 5 2 0 0 0 Example 10 4 1 1 00 Comparative 30 14 11 2 0 Example 1 Comparative 31 16 11 1 0 Example 2Guardian 30 15 10 2 0 Wettable Powder¹⁾ Untreated 80

[0069] TABLE 25 Percentage of infected area(%) Concentration as activeingredients(mg/l) Formulation 1 5 10 50 100 Example 14 16 13 6 0 0Example 15 13 10 8 0 0 Example 16 11 11 5 0 0 Example 17 5 3 1 0 0Example 18 3 3 1 0 0 Example 19 4 2 1 0 0 Example 20 4 3 0 0 0 Example21 9 7 4 0 0 Example 22 8 8 4 0 0 Example 23 8 6 5 0 0 Example 24 9 7 50 0 Example 25 6 3 4 0 0 Example 26 3 2 0 0 0 Example 27 4 2 0 0 0Example 28 5 2 1 0 0 Comparative 21 12 7 1 0 Example 3 Guardian 30 15 102 0 Wettable Powder¹⁾ Untreated 100

[0070] As shown in the above tables, the curative activity of cucumberdowny mildew was also similar to that of tomato and potato late blights.Accordingly, it was confirmed that the fungicidal composition of thepresent invention enhanced both preventive and curing activities ofcucumber downy mildew.

EXPERIMENT 2 Activity of Tank-Mixed Formulations ContainingPolyoxyalkylene Alkyl Ether

[0071] 1) Activity on Tomato Late Blight (Phytophthora infestans)

[0072] A) Preventive Activity

[0073] Tomato seeds were sown in a horticultural bed soil of pots havinga diameter of 6 cm and grown under glass for 4 weeks. Spray liquidshaving the concentrations of 1, 5, 10, 50 and 100 mg/l as activeingredient, respectively, and containing 320 mg/l of polyoxyalkylenealkyl ethers were prepared from the wettable powder of ComparativeExample 1 and polyoxyalkylene alkyl ethers of the following Table 26.The spray liquids were sprayed onto tomato leaves and stems at 5 ml perpot using an atomizer and dried in a greenhouse for 24 hours.Phytophthora infestans was prepared at a concentration of 1×10⁴zoospores/ml and inoculated into the plants using an atomizer. In orderto induce the disease, the inoculated plants were placed at 20° C. underthe relative humidity of 100% for 3 to 4 days. When the incidence rateof disease in the untreated group reached 80% or more, the incidencerate of disease in each group was measured. The results are shown in thefollowing Table 26. TABLE 26 Percentage of infected area(%)Concentration Polyoxyethylene alkyl ether as active ingredient(mg/l)(320 mg/l) in a spray liquid 1 5 10 50 100 Polyoxyethylene(n = 7) 12 8 30 0 lauryl ether(KONION LA-7) Polyoxyethylene(n = 10) 12 6 2 0 0 laurylether(KONION LA-10) Polyoxyethylene(n = 20) 9 7 2 1 0 laurylether(KONION LA-20) Polyoxyethylene(n = 7) 5 2 2 0 0 cetyl ether(KoremulCE-7) Polyoxyethylene(n = 10) 2 2 1 0 0 cetyl ether(Brij 56)Polyoxyethylene(n = 12) 2 0 0 0 0 cetyl ether(Koremul CE-12)Polyoxyethylene(n = 20) 1 1 0 0 0 cetyl ether(Brij 58) Polyoxyethylene(n= 7) 6 3 2 0 0 oleyl ether(Koremul OE-7) Polyoxyethylene(n = 10) 6 5 1 00 oleyl ether(Koremul OE-10) Polyoxyethylene(n = 15) 3 3 0 0 0 oleylether(KONION OA-15) Polyoxyethylene(n = 20) 4 1 0 0 0 oleylether(Koremul OE-20) Polyoxyethylene(n = 7) 7 6 1 1 0 stearylether(Koremul SE-7) Polyoxyethylene(n = 10) 2 1 1 0 0 stearyl ether(Brij76) Polyoxyethylene(n = 14) 1 0 0 0 0 stearyl ether(Koremul SE-14)Polyoxyethylene(n = 20) 2 1 0 0 0 stearyl ether(Brij 78) Polyoxyethylenealkyl ether-free 22 14 5 0 0

[0074] As shown in the above table, the tank-mixed formulationcontaining polyoxyalkylene alkyl ether was confirmed to enhance thepreventive activity of tomato late blight in the same manner as thepremixed one-pack formulation.

[0075] B) Curative Activity

[0076] Tomato seeds were sown in a horticultural bed soil of pots havinga diameter of 6 cm and grown under glass for 4 weeks. Phytophthorainfestans was prepared at a concentration of 1×10⁴ zoospores/ml andinoculated into the plants using an atomizer. In order to induce thedisease, the inoculated plants were placed at 20° C. under the relativehumidity of 100% for 24 hours. Spray liquids having the concentrationsof 1, 5, 10, 50 and 100 mg/l as active ingredient, respectively, andcontaining 320 mg/l of polyoxyalkylene alkyl ethers were prepared fromthe wettable powder of Comparative Example 1 and polyoxyalkylene alkylethers of the following Table 27. The spray liquids were sprayed ontotomato leaves and stems at 5 ml per pot using an atomizer and then, thedisease was induced at 20° C. under the relative humidity of 100% for 2to 3 days. When the incidence rate of disease in the untreated groupreached 80% or more, the incidence rate of disease in each group wasmeasured. The results are shown in the following Table 27. TABLE 27Percentage of infected area(%) Concentration Polyoxyethylene alkyl etheras active ingredient(mg/l) (320 mg/l) in a spray liquid 1 5 10 50 100Polyoxyethylene(n = 7) 16 12 5 0 0 lauryl ether(KONION LA-7)Polyoxyethylene(n = 10) 15 6 3 0 0 lauryl ether(KONION LA-10)Polyoxyethylene(n = 20) 13 5 3 1 0 lauryl ether(KONION LA-20)Polyoxyethylene(n = 7) 5 4 1 0 0 cetyl ether(Koremul CE-7)Polyoxyethylene(n = 10) 3 2 0 0 0 cetyl ether(Brij 56) Polyoxyethylene(n= 12) 2 1 0 0 0 cetyl ether(Koremul CE-12) Polyoxyethylene(n = 20) 2 1 10 0 cetyl ether(Brij 58) Polyoxyethylene(n = 7) 9 8 4 0 0 oleylether(Koremul OE-7) Polyoxyethylene(n = 10) 6 7 4 0 0 oleylether(Koremul OE-10) Polyoxyethylene(n = 15) 5 3 2 0 0 oleylether(KONION OE-15) Polyoxyethylene(n = 20) 5 4 1 0 0 oleylether(Koremul OE-20) Polyoxyethylene(n = 7) 6 5 3 1 0 stearylether(Koremul SE-7) Polyoxyethylene(n = 10) 2 1 0 0 0 stearyl ether(Brij76) Polyoxyethylene(n = 14) 3 1 0 0 0 stearyl ether(Koremul SE-14)Polyoxyethylene(n = 20) 2 1 1 0 0 stearyl ether(Brij 78) Polyoxyethylenealkyl ether-free 43 20 13 3 0

[0077] As shown in the above table, the tank-mixed formulationcontaining polyoxyalkylene alkyl ether was confirmed to enhance thecurative activity of tomato late blight in the same manner as thepremixed one-pack formulation. Accordingly, it was confirmed that thefungicidal composition of the present invention enhanced efficacy notonly in the premixed one-pack formulation but also in the tank-mixedformulation.

EXPERIMENT 3 Activity of the Fungicidal Composition ContainingAdditional Agents for Controlling Plant Diseases Other Than Ethaboxam

[0078] 1) Residual Activity on Tomato Late Blight (Phytophthorainfestans)

[0079] Tomato seeds were sown in a horticultural bed soil of pots havinga diameter of 6 cm and grown under glass for 4 weeks. Spray liquidshaving the concentrations of 100 and 200 mg/l as the product,respectively, were prepared from the wettable powder. The spray liquidswere sprayed onto tomato leaves and stems at 5 ml per pot using anatomizer and dried in a greenhouse for 24 hours. Phytophthora infestanswas prepared at a concentration of 1×10⁴ zoospores/ml and inoculatedinto the plants using an atomizer at 1, 5 and 10 days after spraying theliquids, respectively. In order to induce the disease, the inoculatedplants were placed at 20° C. under the relative humidity of 100%. Theincidence rate of disease was measured at 3 to 4 days after the finalinoculation. The results are shown in the following Table 28. TABLE 28Percentage of infected area(%) Concentration of spray (mg/l; asInoculation day after spraying the liquid Formulation the product) 1 day5 days 10 days Example 32 100 8 10 26 Example 33 7 18 24 Example 34 8 1328 Example 35 8 13 31 Example 36 5 10 13 Example 37 10 10 18 Example 385 13 16 Example 39 6 10 23 Example 40 200 5 8 46 Example 41 13 15 28Example 42 6 11 19 Example 43 1 4 13 Example 44 7 7 20 Example 4 100 109 24 Guardian 7 15 34 Untreated — 100

[0080] As shown in the above table, the combined formulations containingethaboxam and additional agents effective for crop downy mildew or rotexhibited outstanding or similar efficacy even at a lower quantity ofethaboxam, as compared with the formulation of Example 4 and Guardianwettable powder. Especially, the residual activity was remarkablyenhanced in the combined formulation of ethaboxam and mancozeb havingthe effect of preventing various plant diseases. Accordingly, it wasconfirmed that combined formulations containing ethaboxam and otheragents for controlling plant diseases had the enhanced the efficacy. Inparticular, the quantity of ethaboxam which needs to be applied could beremarkably reduced by combining preventive agents with ethaboxam.

EXPERIMENT 4 Relationship of the Concentration of Polyoxyalkylene AlkylEther and Foliar Penetration of Ethaboxam

[0081] In order to investigate the relationship of the concentration ofpolyoxyalkylene alkyl ether and the foliar penetration of ethaboxam,foliar penetration experiment was carried out using radioisotope[C¹⁴]-labeled ethaboxam as follows.

[0082] Cucumber seeds were sown in a horticultural bed soil of potshaving a diameter of 6 cm and grown under glass for 3 weeks. 10 mg ofthe formulation prepared in the comparative example was diluted in 10 mlof tap water. 20 μl of the diluted solution was taken and thereto wasadded 1.0 μCi of ethaboxam labeled with C¹⁴(81.7 μCi/mg) to prepare thediluted ethaboxam formulation labeled with C¹⁴. The diluted solution wasspotted on the foliage of cucumber at a precise amount of 10 μl using amicrosyringe. After spotting, the cucumbers were placed in a greenhousefor 24 hours.

[0083] The plants were cut at a distance of 1 cm from the bottom of soiland the cuts were introduced into 250 ml Erlenmeyer flask. 50 ml of themixed solution of acetonitrile and distilled water (volume ratio=1:4)was added thereto and then, the flask was plugged and shaken for 1minute. Radioactivity of C¹⁴-ethaboxam in the solution was measured witha liquid scintillation counter and the residue was combated with asample oxidizer to collect C¹⁴-carbon dioxide, which was analyzed withthe liquid scintillation counter.

[0084] Foliar penetration of ethaboxam is calculated by subtractingradioactivity in the solution from the total radioactivity, which isidentical with radioactivity in the residue.

[0085] The results are shown in the following Table 29. TABLE 29Formulation Degree of penetration (%) Comparative Example 1 0 Example 110 Example 12 3 Example 13 9 Comparative Example 4 0 Comparative Example5 8 Example 29 15 Example 30 24 Example 31 40

[0086] As can be seen from the above, ethaboxam was hardly penetratedinto plants in the absence of adjuvant and the penetration was increasedin proportion to the content of adjuvant. In addition, it was confirmedthat dispersible concentrate had a higher permeability than wettablepowder. This suggests that enhancement of efficacy is co-related withthe increase of penetration in the presence of polyoxyalkylene alkylether. However, enhancement of efficacy is co-related with, but may notbe proportional to, increase of penetration. That is, the efficacy maybe changed depending on environments within or outside of plants,physiological factors of plants or characteristics of pathogens.

INDUSTRIAL APPLICABILITY

[0087] The fungicidal composition in accordance with the presentinvention not only enhances efficacy of ethaboxam but also reduces itsquantity which needs to be applied thereby to reduce production costs ofactive ingredients and to minimize their quantity applied to theenvironment and thus, contributes to the preservation of agriculturalecosystem.

1. A fungicidal composition which comprisesN-(α-cyano-2-thenyl)4-ethyl-2-(ethylamino)-5-thiazolecarboxamide(ethaboxam)of the formula (I):

, and polyoxyalkylene alkyl ether wherein the weight ratio of ethaboxamto polyoxyalkylene alkyl ether is from about 1:0.5 to about 1:10.
 2. Thecomposition according to claim 1, wherein said polyoxyalkylene alkylether is selected from the group consisting of polyoxyethylene laurylether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether andpolyoxyethylene oleyl ether, each of which has an average of 7 to 20ethylene oxide units per molecule.
 3. The composition according to claim1 which further comprises one or more carriers or surfactants.
 4. Thecomposition according to claim 1 which further comprises one or moreadditional compounds for preventing or curing plant diseases.
 5. Amethod for enhancing the fungicidal activity of ethaboxam whichcomprises adding polyoxyalkylene alkyl ether selected from the groupconsisting of polyoxyethylene lauryl ether, polyoxyethylene cetyl ether,polyoxyethylene stearyl ether and polyoxyethylene oleyl ether, each ofwhich has an average of 7 to 20 ethylene oxide units per molecule, toethaboxam.
 6. A method for controlling undesired phytopathogens whichcomprises applying a formulation prepared from the composition accordingto any one of claims 1 to 4 and containing about 30 to about 300 mg/l ofethaboxam and about 100 to about 2000 mg/l of polyoxyethylene alkylether to target plants.